US5925236A - Processes for visbreaking heavy hydrocarbon feedstocks - Google Patents

Processes for visbreaking heavy hydrocarbon feedstocks Download PDF

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Publication number
US5925236A
US5925236A US08/760,678 US76067896A US5925236A US 5925236 A US5925236 A US 5925236A US 76067896 A US76067896 A US 76067896A US 5925236 A US5925236 A US 5925236A
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United States
Prior art keywords
feedstock
soaker
gas
vessel
walls
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Expired - Fee Related
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US08/760,678
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English (en)
Inventor
Marc Fersing
Luc Gouzien
Elisabeth Mouchot
Geraud Bourley
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Total Marketing Services SA
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Total Raffinage Distribution SA
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Assigned to TOTAL RAFFINAGE DISTRIBUTION S.A. reassignment TOTAL RAFFINAGE DISTRIBUTION S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOURELY, GERAUD, FERSING, MARC, GOUZIEN, LUC, MOUCHOT, ELIZABETH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/007—Visbreaking
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps

Definitions

  • the present invention relates to improvements made to processes and apparatus for visbreaking heavy hydrocarbon feed-stocks.
  • visbreaking a treatment of heavy hydrocarbon feedstocks which comprises placing said feedstocks in the liquid state into a furnace at a temperature sufficient to cause the heaviest hydrocarbons to crack and then introducing them into a maturation device (known in the art as a "soaker") wherein, without additional heating, they travel at a rate such that at the prevailing temperature they have a sufficient residence time for achieving the desired cracking of the heavy molecules into lighter molecules.
  • the cracking results in a reduction in viscosity of the treated feedstock.
  • This process is known as visbreaking (a term of art used as an abbreviation for "viscosity reduction”), and the apparatus used is known as a visbreaker.
  • the soaker usually has the form of a cylindrical enclosure which is not provided with additional means for heating the feedstock and in which, because cracking is endothermic, the feedstock temperature drops a few tens of degrees between the time the feedstock enters the soaker and the time it exits.
  • the temperature in the soaker is generally about 400-500° C. an the pressure about 2 to 30 ⁇ 10 5 pascal.
  • the residence time of the feedstock in the soaker is about 10-30 minutes.
  • the severity, which is a function of the residence time and the soaker temperature, is of the order of 20 minutes.
  • the feedstock to be treated is injected at the bottom of the soaker, whereas the cracked product, including any gaseous products that may have formed, is discharged at the top and is directed to a fractionation unit for atmospheric distillation followed by vacuum distillation.
  • the feedstock to be treated can be a heavy petroleum crude, an atmospheric distillation residue, used only rarely because there are other ways of utilizing it, a vacuum distillation residue or a deasphalting pitch.
  • the visbroken products consist of gaseous hydrocarbons, liquefied petroleum gas, gasoline, gas oil, distillate and visbroken vacuum residue.
  • the visbroken vacuum residue is the last recoverable product and, to be used as fuel oil base, must meet stringent requirements of stability and compatibility with other petroleum fractions. Hence, to meet these requirements, the operator must adjust the visbreaking conditions, particularly the temperature.
  • a major problem encountered in visbreaking units lies in the nonuniform travel of the charge stock inside the soaker and in back-mixing and vortexing, occurring particularly in the vicinity of the side walls and at the bottom of the soaker. These disturbances are aggravated by the gases generated by the cracking reactions and by the fact that the residence time of the feedstock in the soaker varies markedly in the same crosssection, depending on the zone considered. As a result, there is a risk that part of the treated feedstock will be overcracked, while another fraction will be insufficiently cracked.
  • EP-A-007 656 To eliminate this drawback, it has been proposed in EP-A-007 656 to dispose inside the soaker, transversely to the direction of feedstock flow, a plurality of internal structures consisting of perforated plates, the orifices in said plates being circular and/or having the shape of slits, said orifices preferably constituting from 1 to 30% of the plate surface area.
  • each plate causes mixing of the feedstock.
  • the aforecited European Patent Application recommends that from 1 to 20 plates of this type be used in a soaker.
  • Document FR-A-2 528 444 proposes a process for thermal cracking of hydrocarbon oils whereby a fluid, such as steam, is introduced tangentially into the lower part of the soaker (see page 6, lines 8 to 17) through nozzles.
  • a fluid such as steam
  • the purpose of such introduction is to impart rotation to the hydrocarbon feedstock.
  • a purpose of the present invention is to eliminate these drawbacks by use of means suitable for ensuring a more uniform residence time of the feedstock in the soaker and better stability of the visbroken residue.
  • Another purpose of the invention is to limit back-mixing phenomena occurring during treatment of a heavy hydrocarbon feedstock in the soaker of a visbreaking unit.
  • Still another purpose of the invention is to reduce coke formation in visbreaking processes and apparatus.
  • Applicants have, in fact, found that by injecting a gas such as steam or nitrogen into the soaker co-currently, at least in the vicinity of the bottom and the side walls thereof, results at the same time in better feedstock conversion and thus a marked reduction in coke formation, and better stability of the visbreaker vacuum residue.
  • a gas such as steam or nitrogen
  • the invention has as a preferred embodiment a process for visbreaking a heavy hydrocarbon feedstock in the liquid state, comprising bringing said feedstock to an appropriate temperature so as to cause cracking of at least part of the hydrocarbon present, then introducing said feedstock into the bottom part of a soaker wherein the feedstock travels from bottom to top to be discharged at the top of said soaker and directed to a fractionation unit, and injecting a, preferably inert, gas into the feedstock in the soaker in the vicinity of the side walls of the soaker, at least at the bottom of the soaker.
  • This process is characterized in that the gas is injected upward along the side walls of the soaker and flows from bottom to top along said walls co-currently with the hydrocarbon feedstock.
  • the gas by traveling from bottom to top in the vicinity of the soaker walls limits the formation of dead zones and back-mixing in the region of the bottom and the side walls, the residence time of the various fine fluid hydrocarbon streams inside the soaker thus tending to become uniform and to approach the average residence time of the feedstock.
  • the gas has a stripping effect on the products of the charge stock which facilitates the separation of the light products (liquefied petroleum gas, gasoline, gas oil etc.) obtained by conversion in the soaker.
  • Upward gas injection in the vicinity of the walls of the soaker requires only a low gas flow rate which, in particular, eliminates the drawbacks encountered when the process of the abovesaid document FR-A-2 528 444 is used.
  • the flow rate of the injected gas is advantageously from 0.2 to 3 met. tons/h and preferably from 0.5 to 2 met. tons/h.
  • the gas, superheated and at a pressure above that prevailing in the soaker is injected annularly at different injection levels, but the gas can also be introduced into the pipe lines which bring the feedstock to be cracked to the soaker, in which case said gas is introduced upstream of said soaker.
  • Another preferred embodiment of the invention is an apparatus for visbreaking a heavy hydrocarbon feedstock in the liquid state, of the type comprising a means for heating the feedstock to a temperature appropriate for cracking at least part of the hydrocarbons, and a soaker provided at its bottom with at least one feed line for the preheated feedstock and at its top with at least one line through which the treated feedstock is discharged and directed to a unit for fractionating said feedstock, said apparatus being characterized in that it comprises a means for injecting a, preferably inert, gas into the hydrocarbon feedstock to be treated, the injection means being disposed at a location such that inside the soaker the injected gas travels co-currently with the feedstock in the vicinity of the inner face of its side walls, at least at the bottom of the soaker.
  • the gas injection means can contain regularly spaced injection nozzles connected to a source of compressed gas and disposed annularly either along the bottom part of the inner face of the soaker walls or along the bottom of the soaker.
  • Said injection means can also contain a conduit of essentially toroidal shape connected to a source of compressed gas and fitted with regularly distributed gas-discharging orifices, said conduit being disposed in the vicinity of the bottom of the soaker and coaxially therewith.
  • the injection means can also comprise a line for introducing said gas into the heavy hydrocarbon feedstock downstream of the feedstock heating means and upstream of the soaker in the direction of feedstock flow.
  • FIG. 1 is a schematic view of a visbreaking apparatus according to the present invention.
  • line 1 for feeding the heavy hydrocarbon feedstock to be treated in the liquid state
  • furnace 2 through which passes line 1 and which preheats the heavy feedstock to an appropriate temperature to ensure the cracking of at least part of the hydrocarbons it contains;
  • soaker 3 in the form of a closed cylindrical vessel, disposed vertically, which at the bottom is fed through line 1 and which at the top is fitted with line 4 through which the products obtained by cracking the feedstock are discharged and directed to a fractionation unit.
  • a means for injecting a, preferably inert, gas into the hydrocarbon feedstock is provided inside soaker 3, in the vicinity of the bottom and near its side walls.
  • said injection means comprises a conduit 5 of toroidal shape disposed coaxially with the side walls of the soaker at the level of the soaker bottom and which through line 6 is fed with compressed gas.
  • Said conduit 5 comprises regularly spaced orifices through which the compressed gas escapes toward the top of soaker 3, co-currently with the hydrocarbon feedstock. This limits the dead space in the soaker and feedstock back-mixing and prevents coke formation while ensuring stripping of light cracked products present in the soaker.
  • conduit 5 is advantageous if nozzles such as those described in document FR-A-2 528 444 in reference to FIGS. 3A and 3B are to be used, because such use avoids modifying the reactor and thus complicating its utilization.
  • a, preferably inert, gas can be injected under pressure through line 7, represented in the drawing by a broken line, into line 1, downstream of furnace 2 and upstream of soaker 3 in the direction of feedstock flow.
  • line 1 instead would be attached to a peripheral dispersing structure, such as a toroidal conduit (similar to the ring 5, so as to assure upward flow of the gases contained in the feedstock being concentrated along the walls of the soaker 3).
  • a peripheral dispersing structure such as a toroidal conduit (similar to the ring 5, so as to assure upward flow of the gases contained in the feedstock being concentrated along the walls of the soaker 3).
  • the stripping of light cracked products by the injected gas makes it possible to increase the stability of the visbreaker residue. By retaining the same stability value, it is thus possible to increase the degree of feedstock conversion by increasing the soaker temperature.
  • This example illustrates a conventional cracking process whereby a vacuum distillation residue having the following characteristics is subjected to visbreaking without using an auxiliary gas.
  • This vacuum residue was heated to a temperature of about 440° C. in the furnace of a visbreaker unit and then introduced into a visbreaking soaker not modified according to the present invention.
  • Said soaker had a diameter of 2.5 meters and an axial height of 14 meters.
  • the operation was carried out at a temperature of 425° C. and a pressure of 8 ⁇ 10 5 pascal.
  • the flow rate of the feedstock was about 100 met. tons/h and its residence time was of the order of 18 minutes.
  • the visbroken effluent discharged from the soaker was fractionated in an atmospheric distillation column and then in a vacuum distillation column.
  • Example 2 The same vacuum distillation residue as in Example 1 was once again subjected to visbreaking under identical severity conditions.
  • the feedstock was heated in the furnace to a temperature of about 450° C. and the soaker was operated at a temperature of 430° C. and a pressure of 8 ⁇ l0 5 pascal.
  • the soaker was fitted, according to the invention, with a distributor for pressurized steam consisting of a toroidal conduit having a diameter of 30 millimeters and presenting regularly distributed upward-facing orifices. Said distributor rested on the bottom of the soaker and was disposed coaxially with the side walls.
  • the superheated steam was injected at a pressure of 11 ⁇ 10 5 pascal and at a rate of 0.5 met. tons/h, whereas the flow rate of the charge stock was 100 met. tons/h.
  • the residence time of the charge stock was of the order of 15 minutes. In other words, the severity of operating conditions was similar to those of Example 1.
  • the viscosity of the visbreaker vacuum residue was unchanged, but its stability improved, and sediment formation was reduced.
  • Example 1 The same vacuum distillation residue as in Example 1 was subjected to visbreaking under the same severity conditions as in Examples 1 and 2.
  • Example 2 The residue was heated in the furnace to 455° C. and then introduced into the soaker which was equipped with a steam injection ring identical to that of Example 2.
  • the soaker was operated at a temperature of 434° C.
  • the pressure and flow rate conditions of the steam in the soaker were the same as in Example 2.
  • the effluent from the soaker was fractionated first in an atmospheric and then in a vacuum distillation column.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Steroid Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
US08/760,678 1995-12-04 1996-12-04 Processes for visbreaking heavy hydrocarbon feedstocks Expired - Fee Related US5925236A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9514314A FR2741889B1 (fr) 1995-12-04 1995-12-04 Perfectionnements apportes aux procedes et aux dispositifs de viscoreduction de charges lourdes d'hydrocarbures
FR9514314 1995-12-04

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US (1) US5925236A (xx)
EP (1) EP0778331B1 (xx)
JP (1) JP3833318B2 (xx)
CN (1) CN1083876C (xx)
AT (1) ATE185372T1 (xx)
CA (1) CA2191913C (xx)
DE (1) DE69604557T2 (xx)
DK (1) DK0778331T3 (xx)
ES (1) ES2137645T3 (xx)
FR (1) FR2741889B1 (xx)
ZA (1) ZA9610150B (xx)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6533925B1 (en) 2000-08-22 2003-03-18 Texaco Development Corporation Asphalt and resin production to integration of solvent deasphalting and gasification
US20070232845A1 (en) * 2006-03-29 2007-10-04 Baumgartner Arthur J Process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators
US20070232846A1 (en) * 2006-03-29 2007-10-04 Arthur James Baumgartner Process for producing lower olefins
US20100187157A1 (en) * 2006-04-27 2010-07-29 Sunfuu Co., Ltd. Equipment and process for upgrading oil
US8632673B2 (en) 2007-11-28 2014-01-21 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
USD844091S1 (en) 2016-10-20 2019-03-26 Bravo Company Mfg, Inc. Firearm handguard
WO2021127269A1 (en) * 2019-12-19 2021-06-24 Saudi Arabian Oil Company Enhanced visbreaking process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6964199B2 (en) 2001-11-02 2005-11-15 Cantocor, Inc. Methods and compositions for enhanced protein expression and/or growth of cultured cells using co-transcription of a Bcl2 encoding nucleic acid
MY172621A (en) * 2011-05-13 2019-12-06 Catalytic Distillation Tech Method for producing high vcm coke
CN105921079B (zh) * 2016-05-09 2019-01-22 怀化学院 一种含长链氟烷基的聚硅氧烷低聚物裂解的方法
CN110699114B (zh) * 2019-10-23 2020-12-29 东营联合石化有限责任公司 一种改进除水方法的石油炼化常减压装置

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1899889A (en) * 1929-04-25 1933-02-28 Standard Oil Dev Co Eliminating water hazard in treating oils
US2161247A (en) * 1936-06-12 1939-06-06 Texas Co Treating hydrocarbon oil
US2312719A (en) * 1938-11-01 1943-03-02 Standard Oil Dev Co Cracking process
EP0007656A1 (en) * 1978-07-11 1980-02-06 Shell Internationale Researchmaatschappij B.V. Process for the continuous thermal cracking of hydrocarbon oils and hydrocarbon mixtures thus prepared
FR2528444A1 (fr) * 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
US4551233A (en) * 1983-09-02 1985-11-05 Shell Oil Company Continuous thermal cracking process
EP0166604A2 (en) * 1984-06-27 1986-01-02 Fuji Standard Research Inc. Process for thermally cracking heavy hydrocarbon oil
EP0204410A2 (en) * 1985-05-28 1986-12-10 Mobil Oil Corporation Method of supplying heat to high temperature process streams
US4695367A (en) * 1986-03-24 1987-09-22 The M. W. Kellogg Company Diesel fuel production
US4784744A (en) * 1987-09-10 1988-11-15 Mobil Oil Corporation Process for stabilizing intermediates and improving liquid yields and coke quality
US4836909A (en) * 1985-11-25 1989-06-06 Research Association For Residual Oil Processing Process of thermally cracking heavy petroleum oil

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1899889A (en) * 1929-04-25 1933-02-28 Standard Oil Dev Co Eliminating water hazard in treating oils
US2161247A (en) * 1936-06-12 1939-06-06 Texas Co Treating hydrocarbon oil
US2312719A (en) * 1938-11-01 1943-03-02 Standard Oil Dev Co Cracking process
EP0007656A1 (en) * 1978-07-11 1980-02-06 Shell Internationale Researchmaatschappij B.V. Process for the continuous thermal cracking of hydrocarbon oils and hydrocarbon mixtures thus prepared
US4247387A (en) * 1978-07-11 1981-01-27 Shell Oil Company Process for the continuous thermal cracking of hydrocarbon oils
GB2133034A (en) * 1982-06-14 1984-07-18 Neste Oy Procedure for thermal cracking of hydrocarbon oils
FR2528444A1 (fr) * 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
US4551233A (en) * 1983-09-02 1985-11-05 Shell Oil Company Continuous thermal cracking process
EP0166604A2 (en) * 1984-06-27 1986-01-02 Fuji Standard Research Inc. Process for thermally cracking heavy hydrocarbon oil
EP0204410A2 (en) * 1985-05-28 1986-12-10 Mobil Oil Corporation Method of supplying heat to high temperature process streams
US4836909A (en) * 1985-11-25 1989-06-06 Research Association For Residual Oil Processing Process of thermally cracking heavy petroleum oil
US4695367A (en) * 1986-03-24 1987-09-22 The M. W. Kellogg Company Diesel fuel production
US4784744A (en) * 1987-09-10 1988-11-15 Mobil Oil Corporation Process for stabilizing intermediates and improving liquid yields and coke quality

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6533925B1 (en) 2000-08-22 2003-03-18 Texaco Development Corporation Asphalt and resin production to integration of solvent deasphalting and gasification
US20070232845A1 (en) * 2006-03-29 2007-10-04 Baumgartner Arthur J Process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators
US20070232846A1 (en) * 2006-03-29 2007-10-04 Arthur James Baumgartner Process for producing lower olefins
US7718839B2 (en) 2006-03-29 2010-05-18 Shell Oil Company Process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators
US7829752B2 (en) 2006-03-29 2010-11-09 Shell Oil Company Process for producing lower olefins
US20100187157A1 (en) * 2006-04-27 2010-07-29 Sunfuu Co., Ltd. Equipment and process for upgrading oil
US8088273B2 (en) 2006-04-27 2012-01-03 Tapioca-Comercio E Servicos Sociedade Unipessoal Lda Equipment and process for upgrading oil
US8632673B2 (en) 2007-11-28 2014-01-21 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
USD844091S1 (en) 2016-10-20 2019-03-26 Bravo Company Mfg, Inc. Firearm handguard
WO2021127269A1 (en) * 2019-12-19 2021-06-24 Saudi Arabian Oil Company Enhanced visbreaking process
US11149219B2 (en) 2019-12-19 2021-10-19 Saudi Arabian Oil Company Enhanced visbreaking process

Also Published As

Publication number Publication date
DK0778331T3 (da) 2000-02-07
CN1083876C (zh) 2002-05-01
CA2191913A1 (fr) 1997-06-05
JP3833318B2 (ja) 2006-10-11
CN1159474A (zh) 1997-09-17
CA2191913C (fr) 2007-08-21
JPH09183983A (ja) 1997-07-15
DE69604557T2 (de) 2000-03-02
ATE185372T1 (de) 1999-10-15
ZA9610150B (en) 1997-06-17
ES2137645T3 (es) 1999-12-16
EP0778331B1 (fr) 1999-10-06
DE69604557D1 (de) 1999-11-11
EP0778331A1 (fr) 1997-06-11
FR2741889A1 (fr) 1997-06-06
FR2741889B1 (fr) 1999-01-29

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